Stitching of galactomannan when no metal is available. RU patent 2509207.

FIELD: oil and gas industry.

SUBSTANCE: treatment method of an underground formation by fluid involves obtainment of fluid containing a stitching agent of the specified structural formula, which is formed as a result of a reaction of 1,4-benzene diboronic acid with 2-hydroxy-4-aminobenzoic acid, and polysaccharide or material based on cellulose, which involves oxidised functional groups, and injection of fluid to a shaft of a well passing through the formation, and provision of contact of fluid with the formation. Invention has been developed in dependent claims.

EFFECT: improving modification efficiency of viscosity at wide temperature and pressure intervals.

11 cl, 20 ex, 1 tbl, 2 dwg

The technical field to which the invention relates

The present invention, in General, refers to methods and compositions of polymers with desired properties, intended for use in service industry oil fields. In particular, the present invention relates to methods and compositions of polymers with desired properties for modification viscosity oilfield service fluid (fluid).

A known level

The provisions contained in this part apply to the known information relating to the present invention, and may not be known technical solutions.

Guar and derivatives Guara widely used in fluids used in the hydraulic fracturing of the oil wells and for the execution of processes stimulating wells. They are especially used in fluids for hydraulic fracturing , for the initiation and development of hydraulic fracture, to ensure rheological properties during transportation proppant

through a hydraulic fracture, and ensure control over the loss of fluid and proppant placement

in the break after processing cracked up to the closing of cracks wedge material with holding it in place. They are used in combination with several other chemicals, and especially cross-linking agents, with the formation of the optimal stitched gels, required for transportation and accommodation riving material.

Guar used in industry to service the oil fields which can be either a natural gum, or derivationally guar. Derivateservlet the guar can be gidroksipropil (HPG), cationic guar, carboxymethylglucan (CMG), karboksimetilirovaniya (CMHPG), gidroximetilland (HEG), karboksimetilirovaniya (CMHEG), hydrophobically modified guar (HMG), hydrophobically modified carboxymethylglucan (HMCMG) and hydrophobic modified gidroximetilland (HMHEG).

Traditional natural and derivateservlet the guar contain primary and secondary hydroxyl (-OH) group, which are typical functional groups responsible for stitching. In the oil industry inorganic cross-linking agents, such as borates, zirconate, titanates, aluminates, chromates and hafnium, are used to increase viscosity gel. Type inorganic linking agent and conditions used depend on the requirements for fluid environments. Crosslinking agents based on borates are widely used for applications with low to medium temperatures due to their insensitivity shift. It is generally accepted that borate ions responsible for the binding of derivative Guara result of interaction with CIS-hydroxyl in position 2 and 3 of monosaccharides mannose, and galactose. ORGANOMETALLIC crosslinking agents are also used to increase high temperature stability fluid. The complexes of transition metals, such as Zr, Ti, Al, Cr, Hf, widely used as the metallic cross-linking agents. It is generally accepted that organo-metallic ions responsible for the binding Gurovich derivative in the result of the interaction either with CIS-hydroxides in position 2 and 3 of monosaccharides mannose, and galactose, or, in the alternative scenario, with carboxylate groups, entered into the structure of the result derivatization natural guar polysaccharide. Sewn ORGANOMETALLIC agents fluids are typically fluids in slow motion, require appropriate ligands and agents delayed action to achieve acceptable slowing down knitting. ORGANOMETALLIC crosslinking agents are usually more effective when merging derivatives Guara than natural Guara.

In the applications available in the literature on oil production and related to the use Guara and derivatives Guara is a generally accepted fact that all chemical functionality required for effective staple polymer, is available from the source polymer (and this functionality is a hydroxyl group in natural or guar hydroxyl and/or carboxyl group in derivateservlet the guar) prior to its injection into the well bore.

The typical way to use fluid containing these polymers involves the stages of recovery Guara natural or derived Guara in the aquatic environment, the introduction of cross-linking agent and preferably some tools for reducing the interaction between polymer and cross-linking agent. The use of encapsulated cross-linking agents, delayed release activators or the addition of a significant number of competing ligands as agents of complexation with metal linking agent has proved effective methods in many areas of application.

The lack of alternative hydroxyl and/or carboxyl groups, contained in the guar and derivatives Guara, functional chemical fragments impairs the ability of these polymers to interact in the water environment on the other mechanism of reactions of General chemistry. This, in turn, hinders the application of various other organic cross-linking agents used in other industries.

Abad et al. GB2422839B suggested methods functionalization and extra stitching Guara and derivatives Guara by introducing alternative functional groups, such as epoxy or aldehyde, in the main polymer chain Guara.

Applications and ways of staple oxidized Guara containing aldehyde group Guara and similar aldehyde - and carbonyl-containing polymers as a result of chemical reactions on the aldehyde group, proposed earlier. Germino et al. US3297604 proposed to use oxidase enzyme galactose to get oxidized the guar resins, leading to the formation aldegidnymi oxidized products which were custom made by Linoprimer, polyhydroxystearic polymers and proteins. Brady et al. US6022717, described the new method of oxidation Guara using oxidase enzyme galactose. Segura, GB2416792A, suggested a way of processing of underground reservoir machining fluid, containing carbonyl-containing compound and aminecontaining connection. This carbonyl compound may be obtained by oxidation of guar polymer-periodic. Abad et al., GB2422839B, also suggested the use of aldegidnymi polymers, such as polyacrolein, oxidized guar, oxidized starch, guar with grafted acrolein, prioriteringar and polymers containing predecessors aldehyde, such as acetals and hemiacetals, as thickening agents for operations in the well bore. Melbouci et al., US2007/0275862, suggested songs for operations of oil production, including fluid fracturing and stimulation of wells containing and aldehyde obtained by enzymatic oxidation Guara or derived Guara oxidase galactose in combination with catalase and peroxidase.

All Slivochny operations proposed in the known technical solutions, only include the use of functional polymers synthesized out well location and then transported to the well for use in the processing operations to the borehole. In addition, operations are disclosed in the known technical solutions that do not offer methods deceleration of chemical interaction between functional polymer and organic cross-linking agent and are based on the kinetics and diffusion reaction fragments for appropriate regulation of the process of joining. Currently, the slowdown is the determining factor for some downhole operations, such as fracturing, where not slow fluid can cause excessive friction when pumping pipes and inevitably the inability to come up with the speed required, the lack of sufficient width of the crack or unwanted increase in pressure of up to the maximum allowed for processing, in aggregate, may result in a breakdown in the work or claims to quality of service as well. The slowdown in time is also important in applications where there is a mechanism clogging the bottom of a well, such as internal education clay coating, water control, deviations in the wellbore at different stages of processing, variation in natural fractures for directional control of the main wing of hydraulic fracturing or deviation in the layers of different permeability, loss of circulation in the process of drilling, etc. In these applications require a significant increase of viscosity or gelation, once treatment has reached the bottom zone of the wellbore or geological mined seam, to ensure appropriate operation.

In the vast majority of applications in the wellbore where deepening into the wellbore requires the increase of viscosity, stitching and gelation, usually necessary mechanisms slowing down knitting. Essential ways to implement additional deceleration of interaction between functionalized polymers and organic cross-linking agents. The necessary methods for the development of cross-linking systems for modification viscosity systems on the basis of polymers. It is desirable that these methods were effective, cost effective and reliable in a wide interval of temperatures and pressures.

SUMMARY OF THE INVENTION

In some embodiments of the invention disclosed processing methods subsurface strata, providing use of fluid, comprising mainly do not contain metal organic crosslinking agent, selected from a number of compounds such as amines, diamines, poliaminy, polyaminopropyl, alcohols, polyols, polyhydroxylated, hydroxylamine, peptides and proteins, combined with the polysaccharide or cellulosic material containing oxidized functional groups. Then the fluid is injected into the wellbore, passing through the layer, for contact with the reservoir. Polysaccharide or cellulosic material may contain aldehyde group, as one example of oxidized groups, or any other relevant oxidized functional groups. Polysaccharide or cellulosic material can be oxidized when using at least one of the enzymes, oxidizers, photo-oxidation, bacteria, catalyst or other suitable method. Fluid may additionally include inorganic crosslinking agent.

In some cases the aquatic environment is used to obtain fluid is polluted, and the viscosity of the fluid in essence does not change under the effect of impurities contained in the aquatic environment. In addition, in some other cases, the polysaccharide or cellulosic material is at least partially oxidized before restoring or oxidized in the process of recovery in the aquatic environment.

Some other variants of the invention are the ways to obtain fluid, including essentially not containing ORGANOMETALLIC crosslinking agent, selected from a number of compounds such as amines, diamines, poliaminy, polyaminopropyl, alcohols, polyols, polyhydroxylated, hydroxylamine, peptides and proteins, combined with the polysaccharide or cellulosic material that has oxidized in the functional group.

In another embodiment, the invention disclosed way, including the production of fluid, including essentially do not contain metal organic crosslinking agent, selected from a number of compounds such as amines, diamines, poliaminy, polyaminopropyl, alcohols, polyols, polyhydroxylated, hydroxylamine, peptides and proteins, combined with the polysaccharide or cellulosic material that has oxidized functional groups, and then the realization of a contact of the target material with fluid for machining the target zone in the underground reservoir.

BRIEF DESCRIPTION OF DRAWINGS

To further understand some embodiments of the invention and its benefits following are links to the following description is presented in conjunction with the accompanying figures, which

Figure 1 presents a diagram illustrating the first variant of the method,

Figure 2 is a diagram that illustrates the second variant of the method.

DESCRIPTION OF INVENTION

First, it should be noted that the development of any actual implementation of an invention for a particular application should be made numerous implementation - specific solutions for the achievement of specific objectives set by the authors of the invention, such as following

a particular system and procedure of implementation of the business, which will vary from one implementation

to the other. Besides, it is necessary to consider that such an attempt development can be difficult and time consuming, but nevertheless, it will be routine for specialists in this area, possessing the knowledge of the advantages of the present invention. In addition, the composition of used/disclosed in this document may also include some components that are different from those disclosed. Summary of the invention and the present detailed description of each digital value should be considered as modified by the term «approximately», if it has not expressed as modified in this way and also be considered as not modified in such a way, if not specified otherwise in the context. Also in the summary of the invention and present a complete description should understand that the range of concentrations, listed or described as recommended for use, suitable etc. implies that any and every concentration inside the interval, including the target values should be considered as already indicated. For example, the interval from 1 to 10» should be interpreted as including every possible numeric value between approximately 1 and approximately 10. Thus, even if a particular value within the interval, or even do not specify any values within an interval, or mentioned only some specific values, means that the invention authors understand that any and all data values within the range should be considered as these, and that the inventors have information on the suitability of the whole interval and all the values within an interval. The provisions set forth in this document, just give the basic information concerning the present invention, and may not be known technical solutions or describe some of the variants of the invention, illustrating the invention.

Embodiments of the invention described in the present document, are methods of treatment of underground reservoirs using, at least, as part of guar derivatives Guara, functionalized Guara, functional derivatives Guara and preferably oxidized Guara or oxidized derivatives Guara, in particular, with the use of organic compounds in combination with modified polysaccharides, preferably, galactomannan, and more preferably oxidized Guara, obtaining essentially do not contain metal stitched gels, suitable for applications in the development wells, such as, but not limited by them, hydraulic fracturing, deviation, acid melirovanie, pillows killing release, processing, when the loss of circulation, cleaning spiral pipe, control, water purification, thickener, protivovospalitelnym agent, etc. Some advantages include a system that is not dependent on water quality (use of produced water , return water for processing, some types of waste water, sea water or brines high density), early increase of viscosity (i.e. at low temperature without boron) and the effective use/amplified effect of particles and fibers. In some embodiments of the invention or polysaccharide material on the basis of cellulose oxidizes in situ in the course of the operation to adjust the speed and/or time bound.

In one embodiment, the invention described in the figure 1, the method of processing 100 includes the following. Water-soluble polymer 110 «pol-X» (aqueous solution, solid, emulsion, variance)containing functional groups «X», measure the flow of water solvent 120 and essentially reduced to the status described as fluid 130 with linear distribution. At least one thread reactionary chemicals 140 also measure the fluid flow. The flow of organic linking agent «Z-R-Z» 150 containing at least two functional groups «Z» chain bridge «R», also measure the fluid flow. Organic crosslinking agent is a chemical that can interact with polymers in functional groups «Y», but essentially not by functional groups «X», with the formation of relationships «Y-Z-R-Z-Y». May also feed other additives that may be required for efficient processing 160, including, but not limited to, surface-active substances, activators, bactericides, inhibitors swelling of clay, reagents, regulatory filtereddata, emulsifiers, supplements to compensate for the loss of fluid, agents reduce friction modifiers rheological properties, not emulsifying agents, buffers, detergents and additives, inhibitors of H 2 S, inhibitors of paraffin, asphaltenes, acceptors oxygen, modifiers, wettability, agents, lowering the surface tension, regulators iron, total solvent, microemulsions, blowing agents, high-temperature stabilizers, fibers, particles, temporary destructors, inhibitors of inorganic sediments, inhibitors of formation of organic sediments, corrosion inhibitors, secondary, cross-linking agents, etc. Provided sufficient contact time interaction and reaction volume 170 in the way 100 for polymer 110 and reactionary chemicals 140 to turn at least part of some functional groups «X» in the polymer in other functional groups «Y». A chemical interaction between the newly formed groups «Y» functional groups «Z» in organic crosslinking agent 150 accompanied by the formation of viscous, sewn, gel or cured fluid 180 with a sufficient number of points in the formation of organic cross-ties «Pol-Y-Z-R-Z-Y-Pol», able to provide the desired performance downhole action 190. Additional chemical reactions, chemical and/or physical effects, provided other additives 160, can, if necessary, to further increase the viscosity of the fluid and change other rheological properties to ensure that further improve desirable performance properties in the well

190. Specialists in this field will understand that the way 100 provides additional slowdown and essentially improved control of increase of viscosity and the degree of gelation in result of organic reactions of aqueous fluids borehole on the basis of polymeric fluids type Guara and derivatives Guara. Secondary cross-linking agents described in this variant of the invention, are those that are traditionally used for stitching water polymeric fluids used in oil industry, such as cross-linking agents based on compounds of metals such as boron, aluminum, chromium, titanium, hafnium or zirconium, when used in combination with organic cross-linking agents described in this embodiment, the invention.

The most interest polymers for inventions are natural and modified guar gum. Oxidation Guara can be done chemically, or preferably the enzymatic using oxidase galactose. Preferably neutral, anionic or amphoteric guar, which oxidized oxidase galactose, advanced catalase, can be used in combination with oxidase galactose. Oxidase galactose can be put on a firm, suspension or mortar form Gurovich products, for example, ground, powdered, flaky and a tablet form neutral, anionic or amphoteric Garov. Derivationally guar, as that contains gidroksipropil group, can also be used in the oxidized form. Containing aldehyde products can form condensation products with products that have amine or similar functionality.

Starch is a polysaccharide of natural origin, which contains several

aldehydic groups. Polyacrolein is a synthetic polymer, containing one of the aldehyde group on repeating the link. Oxidized polysaccharides obtained in different mechanisms of oxidation, which includes interaction with metals such as osmium, cerium, chromium, manganese, in different oxidation States. Paroxizmalnaya, such as hydrogen peroxide, ions periodic, organic peroxides and persulfates, also be used for oxidation of polysaccharides. The publication of the patent application in the United States the number 2007/0275862 discovered the method of oxidation of the guar resin, enzymatic reaction with enzyme . Although the aim was to improve the yield strength of the polysaccharide found that the presence of numerous aldehydic groups in the chain polysaccharides can be used to improve some typical performance characteristics implemented through the proposed polymer known techniques, such as the use of cross-linking agents on the basis of metals such as boron, aluminum, zirconium, and titanium, for increasing the viscosity of the fluid.

Soft oxidants, enzymes and photocatalytic reactions can be used for oxidation guarav and similar polymers used in the oil fields. Data oxidation reactions can lead to transformation of hydroxyl groups in the carbon atom 6 in the aldehyde group or vicinal hydroxyl groups in the carbon atoms and two aldehyde unlinking carbon-carbon bonds. In addition, oxidation galactose can form aldehydes, ketones and groups of carboxylic acids.

In the known technical solutions according US3297604, GB2416792A, GB2422839B revealed that the presence of organic compounds that can interact with aldehyde groups in the aquatic environment, such as amino compounds compounds (as diamines, poliaminy, polypeptides, etc.) or alcohol-containing compounds (as diols, polyols or derived sugars), provides an effective means of implementing essentially not slow reactions stapling, including aldegidnymi polymers such as polandukraine or prioriteringar, or oxidized guar. For data fluid viscosity regulated mainly on the kinetics of the reaction cross-linkage between amine or alcohol compounds and aldegidnymi connection.

Well-known reaction of condensation of aldehydes with amine functional compounds, such as primary amines. Another advantage of the methods of the present invention consists in the fact that, as disclosed Abad et al. GB2422839B, organic connection between aldehydes, amines can be unstable at the appropriate values of pH and temperature, which leads to unstable relationships, such as-N=CH - or-NH-CH 2 - groups, which can be damaged by prolonged exposure to high temperature, thus providing the emergence samodostatochnaya molecules. This can help to avoid the uncertainty of the effect concentrations time destructor and place proppants considering destruction gels in those areas where this ability to destruction of interest, such as hydraulic fracturing of formations.

Examples of suitable organic cross-linking agents include, but are not limited to, alkylamino, such as Ethylenediamine, Propylenediamine, bytelandian, hexamethylenediamine were, dodecylamine etc. Aromatic diamines, such as 1,4-diaminophenol, also suitable for the implementation of the present invention. Can be used amino acids that contain more than one amino groups, such as arginine or lysine, or more than one atom of nitrogen, such as histidine. Also can be used polypeptides containing many amino groups. Other polyaminoamide compounds such as Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine etc. may also be suitable organic cross-linking agents. Can be used for other amino compounds are water-soluble polymers, such as polifenolami, chitosan, etc.

Examples of some other suitable organic cross-linking agents are ALCALDIA, such as glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc. can Also be used aromatic diols, such as resorcinol. Can be used polyols, such as glycerin, sorbitol, erythritol, or simple sugars, such as glucose, fructose and mannose or galactose. Other polyols, such as polyvinyl alcohol and partially hydrolyzed polyvinyl acetate, are also suitable.

In addition, some of the variants of the invention include partial oxidation of polymers

in the process of recovery of the polymer or before recovery of the polymer. This oxidation will give functional groups (i.e. aldehydes), which can be structured organic cross-linking agents, and may provide for the required initial viscosity. With the passage of fluid through the tubular section of the borehole is appropriate recovery and polysaccharide may even be additionally sewn traditional cross-linking agents based metals (active or delayed action) with maximum viscosity for transportation and accommodation riving material.

Although one task was to provide increasing the viscosity of the fluid at low temperatures, but the authors of the invention it is established that are stable at high temperatures, the fluid can be obtained by introducing advanced in the formulation of cross-linking agents based metals.

Specialists in this field will easily understand that in some cases the use of organic cross-linking agents can lead to improved gel compared to the typical sewn fluids, as the degree of reaction staple less vulnerable to changes in the presence of trace quantities of pollutants in water, such as acid, bicarbonate or bacteria, or even those that occur frequently in untreated water sources or in formation water, resulting in more durable fluids.

In other embodiments of the invention used a cross-linking systems on the basis of non-metals for hardening sewn borate polysaccharide gels or even to reduce the sensitivity to the shift made by compounds of zirconium and titanium polysaccharide gels.

In another embodiment, the invention of a method 200 considered at figure 2, which allows you to type in polymer reaction functional groups that may increase the number of active centers for organic stapling, to provide more active centers for solid metals, change the type of the active centers present in the polymer, and/or can change the strength of joining. Method 200 includes the following operations. There is a source of water-soluble polymer 210 «pol-U» (aqueous solution, solid state, emulsion, variance)containing functional groups «U», which is measured in the flow of a water solvent 220 and essentially hydrated to the state, which will be called liquid 230 with linear distribution. The flow of organic binders with a molecule «V-R-W» 240, containing at least one of stitched group «W»chain bridge «R» and bridge group «V», also measure the fluid flow. This organic molecular binding is defined as chemical that can interact with polymers with functional groups «U» with the formation of links «U " W». At least one thread linking agent XL 250 also measure the fluid flow. Can be ensured supply of other supplements that are required to ensure the effectiveness of treatment 260, including surfactants, activators, bactericides, the inhibitors of swelling clay, agents, regulatory filtrated, emulsifiers, additives to prevent fluid loss, agents, reducing friction, rheology modifiers properties that do not emulsifying agents, buffers, cleaning agents, inhibitors of H 2 S, inhibitors of paraffin, asphaltenes, acceptors oxygen, modifiers, wettability, agents, lowering the surface tension, regulators iron, joint solvent, microemulsions, foaming agents, high-temperature stabilizers, fibers, particles, temporary destructors, inhibitors of inorganic sediments, inhibitors of formation of organic sediments, corrosion inhibitors, secondary, cross-linking agents, etc. Adequate contact, duration, interaction and reaction volume 270 200 way for polymer 210 and chemical binder 240 a transformation, at least, of some functional groups «U» in the polymer into various functional groups «W», creating a functional polymers «pol-U-V-R-W». Chemical interaction between polymers containing the groups «W», and cross-linking agent 250 leads to the formation of viscous, sewn, gel or cured fluid 280 with a sufficient number of points organic matching «Pol-U-V-R-W-m-W-R-V-U-Pol, to provide the required performance in the well 290. Additional chemical reactions, chemical and/or physical effects, provided other additives 260, can, if necessary, to further increase the viscosity of the fluid and change other rheological properties to further enhance desirable performance properties in the well 290. Specialists in this field will understand that the way 200 provides additional deceleration of films and essentially improved control of increase of viscosity and the degree of gelation in result of organic reactions of aqueous fluids borehole on the basis of polymeric fluids such as on the basis Guara and derivatives Guara. Cross-linking agents described in this variant of the invention, are those chemical compounds, which are traditionally used in the oil industry for structuring water polymeric fluids such as cross-linking agents based on compounds of metals such as boron, aluminum, chromium, titanium, hafnium or zirconium.

According to some of the variants of the invention improved the ability to stitch forests can be achieved through the implementation of interaction aldegidnymi polysaccharide polymer chemical compounds that contain amenagraget, which may form the links of " U-V», and can also be achieved improved ability to structure other functional groups «W», such as

(A) amino compounds monosaccharides such as glucosamine, which has several hydroxyl groups, which can be effective centers stapling for compounds of boron; data amino compounds compounds can interact with aldegidnymi polysaccharides with the formation of polysaccharides with side groups that may be more accessible, and/or with more strong complexes with boron than typical mannose residues or galactose Guara and typical derivatives Guara;

(B) amino compounds oligosaccharides, such as amino compounds oligoclase or oligomers, can be used to obtain an anchor groups for stitching Guara or other galactose the xanthan gum, dilanom or other heteropolysaccharides;

(C) functionalized derivatives of aniline, containing a primary amine, such as 1,2-dihydroxy-4-Aminobenzol, 2-hydroxy-4-aminobenzoic acid, 2-Bor-4-aminophenol, 3-Bor-4-gidroximetilland, 3-hydroxy-4-gidroximetilland etc. can be used to create centers for reinforced stitching polysaccharides cross-linking agents containing metal, such as boron or aluminium;

Above the flowing of reaction aimed at the functionalization of polysaccharide, conducted mainly among water-based and can be done as well with the process of mixing in a separate container or at the time of download.

In some embodiments of the invention disclosed molecules that include solid ORGANOMETALLIC communication and which can be used as the extension of cross-linking agents. These molecules will have patterns of General form

X-R 1-Y-M-R 2-M-Y-R 1-X

Patterns can represent, for example, organic structures with diamines terminal groups, which are formed in the reaction seafront Dibrova acid, such as 1,4-bezalabernaya acid (I), 2-hydroxy-4-aminobenzoic acid (II). In this case, X = NH 2 , R 1 = benzene ring from (I), Y = 2-hydroxy-1-carboxypropyl from (II), M = Bronevoi acid and R 2 = benzene ring on (II).

In some embodiments of the invention can be used peptides with the structure of H 2 N-CHR-CO-NH-CHR-CO-) n and similar to it, leading to the formation of custom made parts, which can further increase the movement of particles. Peptide bonds, present in the sewn of molecules, unstable at high temperature and may eventually be destroyed. The length of peptide bonds can be changed to ensure the required stability of the resulting fluid.

The following examples are given to illustrate the method of preparation and properties of some embodiments of the invention, and it should not be construed as limiting the amount of the claims of the invention, if it is not specified otherwise in the appended claims. All interest, concentration, relationships, parts, etc. given by mass, unless otherwise specified or the context clearly in the description of their use.

For some of the following examples have received 1% of mother solution based prioriteringar tar (available from Carbomer Inc.), containing 0.1 mmol aldehyde gram of the guar gum 53 ml of tap water. Received a different fluids according to recipes shown in the examples 1-20, as described in table 1, by dissolving the required reagents in approximately 2 ml specified 1% stock solution prioriteringar resin in the sealed to 4 ml of the glass tube. The reagents used for received in the examples of the compositions were the following connections:

A-1 - sodium hydroxide

A-2 - decahydrate of tetraborate

A-3 - glycerine

A-4 - tsirkonoksidnoj

A-5 - N'-(2-amino-ethyl-N-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine

A-6 - 2,2',2”-nitrilotriethanol

A-7 - 2-aminoethanoles acid

A-8 - hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane

To ensure interoperability between aldehyde groups in prioriteringar resin and amino groups in supplements to the a-7 and a-8, the concentration of these additives, in accordance with the values specified in brackets in table 1, was dissolved in prioriteringar the resin is 15 minutes before adding other chemicals.

Apparent viscosity fluid controlled through various periods of time (1 min, 3 min, 5 min, 10 min and 1 h) to determine changes of the magnitude of the apparent viscosity. Viscosity of each fluid was evaluated according to the following codes and criteria for quantitative estimation of the strength of the gel:

1. The viscosity of the fluid is the same as that of original polymer solution

2. The viscosity of a fluid is a bit higher than the original solution

3. Fluid gel with a substantial degree of crosslinking; easily removed from the tube under the influence of gravity

4. «Spreading the wall» gel flip tubes; difficult to remove from the tube under the influence of gravity.

5. The gel, which almost does not flow when the flip tubes; very difficult to remove from the tube under the influence of gravity

6. Solid gel, which is deformed, but not flowing at the flip tubes; virtually impossible to remove from a test tube under the influence of gravity.

In addition, the speed of gelation (speed increase viscosity fluid) for each fluid evaluated quantitatively. The fluids, which are in full viscosity less than one minute, was assessed as «instant». The fluids, which are in full viscosity less than three minutes, was assessed as «very quick». The fluids, which are in full viscosity less than five minutes, was assessed as «fast». The fluids, which are in full viscosity less than ten minutes, was assessed as «average». The fluids, which are in full viscosity less than one hour, was assessed as «slow». Fluids, not reaching essentially increase viscosity in one hour, was assessed as «N/A».

Table 1 lists the codes gel strength and speed of gelation for compositions, obtained according to the examples 1-20. The concentration of additives are given in the table in %. The concentration of additives a-7, a-8 in parentheses are the number added to a polymer solution within 15 minutes (waiting period) before adding other additives. For examples, 15, 16 and 20 additional concentration of 0.4%, 0.4% and 1.2% Supplement to the a-7 was introduced in 15 minutes after interaction with additives first concentration of 0.5% and polymer.

The composition of fluids is discussed in more detail in the following examples.

Example 1

2.0 ml of solution containing 1% solution prioriteringar resin, were placed in a closed 4 ml glass test tube and watched the changing of viscosity of the fluid in time.

Example 2

2.1 ml of solution containing 1% prioriteringar resin and 0.5% sodium hydroxide, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 3

2.1 ml of solution containing 1% prioriteringar resin, 0.75% of decahydrate of tetraborate sodium and 1.25% of glycerin, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 4

2.2 ml of solution containing 1% prioriteringar resin, 0.5% sodium hydroxide, 0.75% of decahydrate of tetraborate sodium and 1.25% of glycerin, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 5

2.1 ml of solution containing 1% prioriteringar resin, 1.55% 2,2',2”-nitrilotriethanol, 0.3% sodium tetraborate, 0.25% of tsirkonoksidnoj and 0.4% 2-aminophenazone acid, were placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 6

2.2 ml of solution containing 1% prioriteringar resin, 5% N'-(2-amino-ethyl-N-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine, 1.55% 2,2',2”-nitrilotriethanol, 0.3% sodium tetraborate, 0.25% of tsirkonoksidnoj and 0.4% 2-aminophenazone acid, were placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 7

2.1 ml of solution containing 1% prioriteringar resin, 5% N'-(2-amino-ethyl-N-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 8

2.1 ml of solution containing 1% prioriteringar resin and 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 9

2.2 ml of solution containing 1% prioriteringar resin, 0.5% sodium hydroxide and 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 10

2.3 ml of solution containing 1% prioriteringar resin, 0.5% sodium hydroxide, 0.75% of decahydrate of sodium tetraborate, 1.25% glycerol and 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 11

2.3 ml of solution containing 1% prioriteringar resin, 5% N'-(2-amino-ethyl-N-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine, 1.55% 2,2',2”-nitrilotriethanol, 0.3% sodium tetraborate, 0.25% of tsirkonoksidnoj, 0.4% 2-aminophenazone acid and 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 12

2.2 ml of solution containing 1% prioriteringar resin, 1.55% 2,2',2”-nitrilotriethanol, 0.3% sodium tetraborate, 0.25% of tsirkonoksidnoj, 0.4% 2-aminophenazone acid and 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 13

2.3 ml of solution containing 1% prioriteringar resin, 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane and 5% N'-(2-amino-ethyl-N-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 14

2.1 ml of solution containing 1% prioriteringar resin and 0.5% 2-aminophenazone acid, were placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 15

2.3 ml of solution containing 1% prioriteringar resin, 5% N'-(2-amino-ethyl-N-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine, 1.55% 2,2',2”-nitrilotriethanol, 0.3% sodium tetraborate, 0.25% of tsirkonoksidnoj, 0.9% 2-aminophenazone acid, were placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 16

2.2 ml of solution containing 1% prioriteringar resin, 1.55% 2,2',2”-, 0.3% sodium tetraborate, 0.25% of and 0.9% 2- acid, were placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 17

2.3 ml of solution containing 1% prioriteringar resin, 5% N'-(2-amino-ethyl-N-[2-(2-)ethyl]ethane-1,2-diamine and 0.5% 2- acid, were placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 18

2.5 ml of solution containing 1% prioriteringar resin, 0.5% sodium hydroxide, 2.25% decahydrate of sodium tetraborate, 3.75% glycerol and 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 19

2.4 ml of solution containing 1% prioriteringar resin, 4.65% 2,2',2”-nitrilotriethanol, 0.9% sodium tetraborate, 0.75% of oxizilor of zirconyl, 1.2% 2-aminophenazone acid and 5% hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane, was placed in a closed 4 ml glass test tube and watched the changing of viscosity of a fluid over time.

Example 20

The strength of the gel and the speed of gelation for compositions of fluid obtained according to the examples 1-20

The strength of the gel

The speed of gelation

Very high

Very high

(0.5)+0.4

(0.5)+0.4

(0,5)+1,2

A comparison of examples 1-20 shows that aldehyde - and hydroxyl-containing polymer prioriteringar resin itself does not condense at high pH values (brought sodium hydroxide). A comparison of examples 1 and 2 for example, 7 indicates that the insignificant increase of viscosity due to the reaction of structuring between aldegidnymi polymer and poliaminy additive And 5.

Examples 3 and 4 show that the polymer prioriteringar resin able to form structured borate gels. Examples 5 and 6 show that the polymer prioriteringar resin able to form structured Bor-zirconate cross-linking agents gels. A comparison of examples 3 and 5, 4 and 6 shows that stronger structured borate gels can be obtained by using Bor-zirconate structuring agent than using pure borate fluid even at lower concentrations of boron.

A comparison of examples 1, 8, 9 and 14 shows that the reaction of condensation between aldegidnymi polymer and monoaminoxidase addition to the a-7 (with side hydroxyl groups) or a-8 side carboxyl groups) does not structuring, nor to any increase in the apparent viscosity.

A comparison of examples 7 and 13 shows that the reaction of condensation between aldegidnymi polymer and monoaminoxidase addition to the a-7 (with side hydroxyl groups) reduces further interaction aldehyde polymer with Polyamin A-5, indicating that a significant number of source aldehydic groups reacted with amine groups supplements to the a-7 in the course of 15-minute delay to education, thus, polymers with new additional side hydroxyl functional groups that do not form cross-links with Polyamin A-5.

From a comparison of examples 7 and 17 shows that the reaction of condensation between polymer and addition to the a-8 side carboxyl groups) - reduces further interaction aldehyde polymer with A-5, indicating that a significant number of source aldehydic groups reacted with amine groups additives And 8 during the 15-minute delay to education, thus, polymers with new side carboxyl functional groups that will not form cross-links with A-5.

The results obtained for examples 10, 11 and 12 show that the modified polymer containing side of the hydroxyl group, obtained according to the example 8, still retain the ability to interact with typical borate or boron-zirconate cross-linking agents. A comparison of examples 10, 11 and 12 with examples 4, 5 and 6 shows that the rate of gelation below for the first compared to last. This is caused by an excess of unreacted supplements a-8, which belongs to the class of chemical compounds, known as connections, delaying or reducing the degree of structuring borate at the expense of complex formation with Borat-ion.

To confirm the possibility of the formation of fluid and better structured polymer containing side hydroxyl groups are formed by condensation of prioriteringar resin and aminecontaining polyol And 7, the concentration of the cross-connections have increased in the examples of 18th and 19th. A comparison of examples of 18th and 19th examples 10 and 12 shows that the change of concentration of linking agent can get really more structured gels (with higher strength gel) and higher speeds stitching.

The results obtained for examples 15 and 16 show that the modified polymer containing side carboxyl groups, obtained according to the example 14, still retain the ability to interact with typical borate or boron-zirconate cross-linking agents. A comparison of examples 15 and 16 in examples 5 and 6 shows that the rate of gelation below for the first compared to last. This is caused by an excess of unreacted additives And 7, which belongs to the class of chemical compounds, known as connections, delaying or reducing the degree of structuring the lead zirconate at the expense of complex formation with the lead zirconate-ion.

To confirm the possibility of formation fluid with improved structuring of polymer containing side carboxyl groups, formed by condensation prioriteringar resin and aminecontaining polycarboxylic acids And 7, the concentration of the cross-connections increased in 20 examples. A comparison of examples of 20, with examples, 15 and 16 shows that the change of concentration of linking agent can get really more structured gels (with higher strength gel) and higher speeds stitching.

Specialists in this field will easily understand that the degree of response modification solution prioriteringar resin hydrochloride 2-amino-3,4,5,6-tetrahydroxyhexane (Supplement a-8), shown in the above examples, may be subject to stoichiometry (relationship aldehydic groups to amine)response time (timeout), and the temperature at which carry out the reaction. Similarly, it is also easy to understand that the degree of response modification solution prioriteringar resin 2-aminophenazone acid (Supplement a-7), shown in the above examples, can also be regulated by the stoichiometry (relationship aldehydic groups to amine)response time (timeout), and the temperature at which carry out the reaction. Stoichiometry and reaction time are the parameters that can be easily adjusted in the process operation of the wellbore by modifying the concentration of additives to raw materials and consumption of fluid for processing. In addition, the temperature can first be modified by changing the temperature of the water brine and additionally by changing the flow of the fluid for processing, ensuring a longer or shorter period of contact layers surrounding the wellbore.

Specific examples of embodiments of the invention described above are only explanatory, since the invention can be modified and implemented different but equivalent ways obvious to specialists in this area, as have knowledge of the benefits of the provisions of this document. In addition, there are no restrictions on the items shown in this document, other than those described below in the claims. So, obviously, the above specific embodiments of the present invention may be altered or modified, and all of these changes are discussed in the volume of claims and the essence of the present invention. Accordingly, this document is sought protection in accordance with the attached below the claims.

1. The way of processing of underground reservoir fluid, the method includes a) receive fluid containing the i. crosslinking agent:

that is formed from the reaction of 1,4-bezalabernaya acid with 2-hydroxy-4-aminobenzoic acid, and ii. or polysaccharide material on the basis of cellulose containing oxidized functional group; and b) the introduction of fluid in the borehole, passing through the formation and ensuring the contact of fluid reservoir.

2. The method of claim 1, where polysaccharide or material on the basis of cellulose includes aldehyde group.

3. The method according to any of the preceding paragraphs, where the fluid also contains inorganic crosslinking agent to achieve deceleration stitching and stability at high temperatures.

4. The method according to any of claims 1 or 2, where the fluid is samodestruktivnost.

5. The method according to any of claims 1 or 2, where the fluid has a pH of between about 2 and 9, and where treatment is one such operation, as hydraulic fracturing, acid fracturing, gravel packing, processing cracks and gravel packing, hole-cleaning or use of obscure pillows.

6. The method according to any of claims 1 or 2 to get a fluid applied water environment, where water contains impurities and where the viscosity of the fluid has not significantly changed under the action of pollutants contained in the water environment.

7. The method according to any of claims 1 or 2, where polysaccharide or material on the basis of cellulose, at least partially oxidized before restoring or during recovery in the aquatic environment.

8. The method according to any of claims 1 or 2, where polysaccharide or material on the basis of cellulose is oxidized by using at least one of the enzymes, oxidizers, photo-oxidation, bacteria or catalyst.

9. The method according to any of claims 1 or 2, where polysaccharide or material on a basis cellulose is the polymer structure of the polymer-Z-X.

10. The method according to claim 1 or 2, where polysaccharide or material on the basis of cellulose has polulegalny functionality suitable for stitching ORGANOMETALLIC cross-linking agent.